CN113583374A - Preparation method of nanoscale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene - Google Patents
Preparation method of nanoscale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene Download PDFInfo
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Abstract
The invention provides a preparation method of environment-friendly flame-retardant low-smoke high-impact polystyrene resin. Firstly, adding conjugated diene and aryl ethylene compounds to prepare a super-dispersed high-molecular functionalized composite nano smoke suppressant by an in-situ polymerization method; secondly, synthesizing a high-molecular flame retardant of phosphorus-nitrogen by using a micromolecular flame retardant of allyl phosphodiester, vinyl amide, 1, 3-butadiene and styrene; finally, directly blending and granulating the high-molecular phosphorus-nitrogen flame retardant, the ultra-dispersed high-molecular functional composite nano smoke suppressant and the high impact polystyrene resin to prepare the environment-friendly flame-retardant low-smoke high impact polystyrene resin with the maximum smoke density of less than 70, the oxygen index of more than 47 percent and the cantilever beam notch impact strength of more than 14kJ/m 2. The method endows the HIPS resin with the characteristics of environmental protection, no pollution, low smoke generation, high flame retardance and the like.
Description
Technical Field
The invention relates to a preparation method of environment-friendly flame-retardant low-smoke high-impact polystyrene resin, in particular to a preparation method of high-impact polystyrene resin modified by a high-molecular phosphorus-nitrogen flame retardant and a super-dispersed high-molecular functional nano smoke suppressant.
Background
High Impact Polystyrene (HIPS) has the advantages of excellent formability, good toughness, high dimensional stability, good electrical insulation performance, easy dyeing, low moisture absorption, low price and the like, is widely applied to the industries of packaging, electronics, buildings, automobiles, household appliances, instruments, daily necessities, toys and the like, and becomes one of the fastest-developing varieties of the current general synthetic resins. However, as a common disadvantage of general polymer materials, HIPS also has problems of easy combustion, fast flame propagation during combustion, and the like, and the application thereof is greatly limited in environments with high temperature requirements. At present, nearly 80% of fire retardants used in China are halogen-containing fire retardants, but in recent years, halogen-containing fire retardants generate a large amount of smoke, dioxin, corrosive gas and other problems during combustion, and cannot meet the requirement that European Union issues' directive (ROHS for short) about prohibition of use of certain harmful substances in electronic and electrical equipment in 2003, so that domestic electric appliances from China will be rejected by the European Union market. Therefore, China must develop green and environment-friendly halogen-free flame retardant materials vigorously to adapt to the development trend of the international market.
In the prior art, the research on halogen-free flame retardant of high impact polystyrene resin is mainly prepared by adding inorganic and organic halogen-free flame retardants. Such as: ZL201110098731.0 discloses a magnesium hydroxide flame retardant with surface treated by sulfonated high impact polystyrene, which is mixed with high impact polystyrene resin to prepare a flame retardant with impact strength of 5.4kJ/m2And 29% oxygen index. CN201910089719.X discloses a flame retardant micro-foamed polyphenylene ether composite material prepared by mixing and blending an organic phosphorus flame retardant, inorganic hypophosphite, polyphenylene ether and high impact polystyrene. CN 111518355A discloses a method for preparing a flame-retardant high impact polystyrene composite material by using a silane coupling agent modified phosphorus flame retardant ammonium polyphosphate and a nano flame retardant carbon nano tube. Polybutadiene/silicon dioxide nano composite material is prepared by a single swallowwort root through an anion in-situ polymerization method, the surface of a nano white carbon black particle is treated by Y-methyl-acryloyloxy-propyl-trimethoxysilane (MPS), then modified silicon dioxide is dispersed in a butadiene and pentane solvent, n-butyl lithium is added as an initiator after high-sound dispersion, polymerization reaction is carried out under the protection of nitrogen, then a product is added into ethanol to obtain a white precipitate, and the white precipitate is filtered and dried to obtain the modified silicon dioxide nano composite material (the synthetic rubber industry, 2006,29(6): 474).
The patents adopt small-molecular organic and inorganic powder halogen-free flame retardants for modification, although obvious effects are achieved in the aspect of improving the flame retardance of HIPS resin, the surface properties of the halogen-free flame retardants and nano inorganic materials are far different from those of the HIPS resin, the problem of easy agglomeration and dispersion of nano inorganic powder is difficult to solve only through the traditional modification methods such as mechanical stirring or coupling agent surface treatment, the consumption of the flame retardants is large on the premise of ensuring the flame retardance, the mechanical property of the HIPS resin is greatly reduced, and the balance between the flame retardance and the mechanical property of the HIPS resin cannot be realized.
Disclosure of Invention
The invention aims to provide a high-performance high-smoke-density high-oxygen-index high-oxygen-content high-strength high-smoke-density high-oxygen-index high-density high-oxygen-index high-density high-oxygen-index high-density high-oxygen-index high-oxygen-index high-density2The preparation method of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin. Firstly, carrying out composite amination treatment on a nano smoke suppressant, then coating a polar monomer vinyl amide of vinyl amide to form reaction seeds, and then adding conjugated diene and aryl ethylene compounds to prepare a super-dispersed high-molecular functionalized nano smoke suppressant by an in-situ polymerization method; secondly, synthesizing a high-molecular flame retardant of phosphorus-nitrogen by using a micromolecular flame retardant of allyl phosphodiester, vinyl amide, 1, 3-butadiene and styrene; and finally, directly blending and granulating the macromolecular phosphorus-nitrogen flame retardant, the ultra-dispersed macromolecular nano smoke suppressant, the ultra-dispersed macromolecular functional nano smoke suppressant and the high impact polystyrene resin to prepare the environment-friendly flame-retardant low-smoke high impact polystyrene resin. The method realizes the high polymerization and super dispersion of the flame retardant and the nano smoke suppressant, greatly improves the compatibility of the flame retardant and the nano smoke suppressant with High Impact Polystyrene (HIPS) resin, avoids the damage of the nano smoke suppressant to the mechanical property of the HIPS resin, fully exerts the synergistic effect and the superfine effect of the high polymerization flame retardant and the nano smoke suppressant, and endows the HIPS resin with the characteristics of environmental protection, no pollution, low smoke generation and high flame retardance.
The "parts" in the present invention mean parts by mass.
The preparation of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin is carried out in a reaction kettle and a screw kneading machine, and the preparation steps are as follows:
(1) ultra-dispersed polymer functionalized nano smoke suppressant: according to 100 parts of the total mass of the nano smoke suppressant, firstly introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 300-400 parts of solvent and 1-5 parts of polyamine into the polymerization kettle, adjusting the pH value of the system to 8.0-9.0 by using a buffering agent, adding 100 parts of nano smoke suppressant and 1.0-3.0 parts of silane coupling agent when the temperature is raised to 50-60 ℃, stirring and mixing for 1.0-2.0 hours, then adding 5-10 parts of vinyl amide, stirring and mixing for 2.0-3.0 hours to generate seeds which are coated by vinyl amide monomers by taking inorganic nano smoke suppressant powder as the center and can be copolymerized; and finally, sequentially adding 20-30 parts of conjugated diene and 10-20 parts of aryl ethylene compound, heating to 70-80 ℃, adding 0.05-0.3 part of initiator, reacting for 5.0-7.0 hr, then adding 1-5 parts of terminator, washing, drying and grinding to obtain the ultra-dispersed high-molecular functionalized nano smoke suppressant.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: based on 100 parts of total mass of allyl phosphate diester and vinyl amide, firstly introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent, 70-80 parts of allyl phosphate diester, 20-30 parts of vinyl amide and 0.1-0.5 part of molecular weight regulator into the polymerization kettle, stirring, mixing and heating, adding 0.05-0.5 part of initiator a when the temperature of the polymerization kettle reaches 60-70 ℃, reacting for 5.0-7.0 hr, then adding 5.0-10.0 parts of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50-70 min until no free monomer exists, and washing and drying to prepare the macromolecular phosphorus-nitrogen flame retardant with reactivity.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: based on 100 parts by mass of the macromolecular phosphorus-nitrogen flame retardant, firstly introducing inert gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2-4 times, sequentially adding 200-300 parts of solvent and 100 parts of macromolecular phosphorus-nitrogen flame retardant with reaction activity into the reaction kettle,0.05 to 0.1 part of structure regulator and 0.05 to 70 parts of initiator b, heating to 60 to 70 ℃, and reacting for 50 to 80min to form [ -BR-]nMacromolecular "phosphorus-nitrogen" flame retardants for homopolymers; and then sequentially adding 20-30 parts of styrene and 0.05-0.2 part of structure regulator into the polymerization kettle, heating to 70-80 ℃, reacting for 70-90 min, adding 1.0-5.0 parts of terminator, finally discharging, washing and drying to obtain the high-molecular phosphorus-nitrogen flame retardant.
(3) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: taking 100 parts of high impact polystyrene resin, adding 100 parts of high impact polystyrene resin, 5-15 parts of high molecular phosphorus-nitrogen flame retardant, 5-10 parts of ultra-dispersed high molecular functional nano smoke suppressant, 0.2-0.6 part of stabilizer and 0.1-0.5 part of antioxidant into a high-speed mixer, and mixing for 5-10 min; and then directly adding the mixed materials into a double-screw extruder, reacting at 160-200 ℃ for 4-6 min, extruding, cooling and granulating to obtain the environment-friendly flame-retardant low-smoke high-impact polystyrene resin.
The macromolecular phosphorus-nitrogen flame retardant has the following structural general formula:
in the formula: r is C1～C8Alkyl groups of (a); PS is a homopolymer of styrene; BR is a homopolymer of 1, 3-butadiene. The allyl phosphate diester is one of dimethyl allyl phosphate, diethyl allyl phosphate, dipropyl allyl phosphate, dibutyl allyl phosphate, dipentyl allyl phosphate, dihexyl allyl phosphate, diheptyl allyl phosphate and dioctyl allyl phosphate, and preferably diethyl allyl phosphate. The vinyl amide polar monomer is one selected from acrylamide, methacrylamide, 1-butene amide, methacrylamide, 1-hexene amide and N-propenyl aniline, and N-propenyl aniline is preferred.
The high impact polystyrene is a copolymer (HIPS) of styrene and polybutadiene rubber, can be powdery or granular resin, and has a Melt Flow Rate (MFR) of 0.5-20 g/10 min.
The nano smoke suppressant is selected from one of carbon nano tube, graphene oxide or nano white carbon black, and preferably the nano white carbon black.
The polyamine in the invention is selected from one of ethylenediamine, triethylamine, diethylenetriamine, hexamethylenetetramine and isophoronediamine, and preferably ethylenediamine.
The conjugated diene is selected from 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2, 3-diethyl-1, 3-butadiene, 2-methyl-3-ethyl-1, 3-butadiene, 1, 3-pentadiene and 3-butyl-1, 3-octadiene; 1, 3-hexadiene, preferably 1, 3-butadiene.
The aryl ethylene compound can be one of styrene, alpha-methyl styrene and 2-phenylpropylene, and styrene is preferred.
The initiator a is an organic peroxide, and is selected from one of di-tert-butyl hydroperoxide (TBHP), 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide (BPDH), di-tert-butyl peroxide (DTBP) and dicumyl peroxide (DCP), preferably BPDH.
The initiator b is a hydrocarbyl monolithium compound selected from one of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, lithium naphthalene, cyclohexyllithium and dodecyllithium, preferably n-butyllithium.
The molecular weight regulator of the present invention may be selected from one of tertiary dodecyl mercaptan, tertiary tetradecyl mercaptan and tertiary hexadecyl mercaptan, and tertiary dodecyl mercaptan is preferred.
The structure regulator of the invention is a polar organic compound which generates solvation effect in a polymerization system and can regulate the reactivity ratio of styrene and butadiene. Such polar organic compound is selected from one of diethylene glycol dimethyl ether (2G), Tetrahydrofuran (THF), diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether (DME), triethylamine, preferably Tetrahydrofuran (THF).
The silane coupling agent of the present invention may be one selected from the group consisting of gamma-aminopropyltriethoxysilane (KH-550), 3-glycidoxypropyltrimethoxysilane (KH-560), vinyltriethoxysilane (A-151), N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602), gamma-methacryloxypropyltrimethoxysilane (KH-570), N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792), vinyltrimethoxysilane (A-171), vinyltris (beta-methoxyethoxy) silane (A-172), preferably KH-550.
The screw kneader according to the invention can be a single-screw extruder or a multi-screw extruder, preferably a twin-screw extruder.
The nitrogen and argon used as the displacement gas of the polymerizer in the present invention may be replaced with one of other group 0 rare gases other than radon.
The solvent, antioxidant, stabilizer, terminating agent and buffering agent are not limited in particular, and conventional auxiliary agents commonly used in the art can be used, for example, the solvent is a hydrocarbon solvent selected from one of pentane, hexane, octane, heptane, pentane, benzene, toluene, xylene and ethylbenzene. The antioxidant is one of phenol, hindered amine and phosphite diester. The stabilizer is stearate, such as zinc stearate or calcium stearate. The terminating agent may be selected from one or more of diethylhydroxylamine, hydroxylamine sulphate, sodium ferbamate, methanol and ethanol. The buffering agent can be one selected from sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water and ammonium bicarbonate, and sodium hydroxide is preferred.
Firstly, carrying out amination treatment on the surface of a nano smoke suppressant by using a silane coupling agent and polyamine to enable the surface of inorganic particles to have amino groups, enabling the amino groups and the amino groups in vinyl amide monomers to have strong mutual attraction effect, forming seeds of vinyl amide reaction monomers on the surface of the nano smoke suppressant, and then generating a layer of block copolymer coating of poly-conjugated diene and aryl ethylene on the surface of the nano smoke suppressant particles by using conjugated diene and aryl ethylene compounds through an in-situ polymerization method to prepare the ultra-dispersed high-molecular functional nano smoke suppressant. The nano smoke suppressant mainly plays two roles: on one hand, the coating layer has the coupling effect, greatly improves the compatibility of the nano smoke suppressant and the high impact polystyrene resin, and mainly has the characteristics of nonpolar and PS chain structure, so that the surface energy of inorganic nano smoke suppressant particles can be obviously reduced, the mutual agglomeration among the particles is hindered, the particles can be stably and uniformly dispersed in a HIPS resin matrix in a single particle form, and the effect of blocking heat and gas is better exerted. On the other hand, the coating layer plays a toughening role, and the coating layer mainly contains a certain amount of polybutadiene chain segments with 1,4 structures, so that the reduction of the impact resistance of HIPS resin caused by the introduction of rigid inorganic nano smoke suppressant is avoided, and the impact resistance is also improved. Secondly, the invention adopts micromolecule flame retardant allyl phosphodiester, vinyl amide and 1, 3-butadiene for copolymerization to prepare the macromolecular phosphorus-nitrogen flame retardant with reactivity, and then the macromolecular phosphorus-nitrogen flame retardant is prepared by solution polymerization with styrene under the initiation of n-butyl lithium. The macromolecular flame retardant not only improves the synergistic effect of the phosphorus-nitrogen flame retardant, but also avoids the migration and precipitation of the micromolecular flame retardant in the high impact polystyrene resin matrix, improves the high efficiency and the durability of the flame retardant effect, and simultaneously does not contain a halogen flame retardant, thereby avoiding the harm of a large amount of corrosive and toxic smoke gas to human bodies and environment caused by the halogen flame retardant during combustion.
Therefore, the synergistic effect generated by the ultra-dispersed high-molecular functional nano smoke suppressant and the high-molecular phosphorus-oxygen flame retardant endows the HIPS resin with environmental protection, high efficiency and durability of flame retardance and smoke suppression performance, not only solves the problem of balance of flame retardance and mechanical property of the HIPS resin, but also improves the impact resistance of the HIPS resin, and the prepared HIPS resin has the maximum smoke density of less than 70, the oxygen index of more than 47 percent and the notched impact strength of a cantilever beam of more than 14kJ/m2The environment-friendly flame-retardant low-smoke high-impact polystyrene resin. The method has the characteristics of environmental protection, good smoke suppression efficiency, high flame retardant efficiency, low modification cost and the like.
Detailed Description
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The "parts" described in examples and comparative examples each refer to parts by mass.
Firstly, raw material sources:
high impact polystyrene (HIPS, 492J), MFR: 2.9g/10min, China petrochemical Yanshan petrochemical Co
Solution polymerized styrene-butadiene rubber cement (SSBR2564s) with a solid content of 10%, of the oil-independent petrochemical company of China
Allyl diethyl phosphate, 98% purity, Shanghai Mirui chemical technology Co., Ltd
N-propenyl aniline of 99% purity, Shanghai Miruil chemical technology Co., Ltd
Styrene, Polymer grade, Petroleum Lanzhou petrochemical Co, China
1, 3-butadiene, polymer grade, petroleum landification, Inc. of China
Nano white carbon black with particle size of 30-100 nm Weifang Wanli auxiliary agent Limited company
N-butyl lithium, 98% purity Nanjing Tongtiang chemical Co., Ltd
2, 5-dimethyl-2, 5-di-tert-Butylperoxyhexane (BPDH), Lanzhou auxiliary plant
Other reagents are all commercial products
The method comprises the following steps:
determination of oxygen index: the assay was carried out as described in GB 10707-1989.
Measurement by vertical Combustion method: the assay was carried out as described in GB/T13488-1992.
Determination of the maximum smoke density: the assay was carried out as described in GB/T8323-1987.
Determination of notched Izod impact Strength: according to GB/T1843-1996.
Example 1
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of pentane and 10g of ethylenediamine into the polymerization kettle, adjusting the pH value of a system to be 8.0 by using sodium hydroxide, adding 1000g of nano white carbon black and 10g of KH-550 into the polymerization kettle when the temperature is raised to 50 ℃, stirring and mixing for 1.0hr, then adding 50g of N-propenyl aniline, stirring and mixing for 2.0hr to generate seeds which are coated by the N-propenyl aniline monomer and can generate copolymerization, wherein the inorganic nano smoke suppressant powder is used as the center; finally, 200g of 1, 3-butadiene and 100g of styrene are sequentially added, 0.5g of BPDH is added when the temperature is raised to 70 ℃, the reaction is carried out for 5.0hr, then 10g of diethylhydroxylamine is added, and the ultra-dispersed polymer functionalized nano smoke suppressant is prepared by washing, drying and grinding.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of pentane, 700g of diethyl allylphosphate, 300g of N-propenyl aniline and 1g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 0.5g of BPDH when the temperature of the polymerization kettle reaches 60 ℃, reacting for 5.0hr, then adding 50g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50min, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: firstly, introducing inert gas into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2000g of pentane, 1000g of macromolecular phosphorus-nitrogen flame retardant, 0.5g of THF and 5.0mmo1 of n-butyllithium into the reaction kettle, heating to 60 ℃, and reacting for 50min to form [ -BR-]nMacromolecular "phosphorus-nitrogen" flame retardants for homopolymers; then adding 200g of styrene and 0.7g of THF into a polymerization kettle in sequence, heating to 70 ℃, reacting for 70min, adding 10g of methanol, discharging, washing and drying to obtain the high-molecular phosphorus-nitrogen flame retardant.
(3) The preparation of the nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following steps: 2000g of HIPS (492J), 100g of high-molecular phosphorus-nitrogen flame retardant, 100g of ultra-dispersed high-molecular functional nano smoke suppressant, 6g of zinc stearate and 10104 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 5min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 2
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the same as in example 1.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 1.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 1.
(3) The preparation of the nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following steps: 2000g of HIPS (492J), 150g of high-molecular phosphorus-nitrogen flame retardant, 130g of ultra-dispersed high-molecular functional nano smoke suppressant, 8g of zinc stearate and 10105 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 6min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 3
(1) Ultra-dispersed polymer functionalized composite nano smoke suppressant: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2600g of pentane and 30g of ethylenediamine into the polymerization kettle, adjusting the pH value of a system to be 8.5 by using sodium hydroxide, adding 1000g of nano white carbon black and 20g of KH-550 into the polymerization kettle when the temperature is raised to 55 ℃, stirring and mixing for 1.5 hours, then adding 70g of N-propenyl aniline, stirring and mixing for 2.6 hours to generate seeds which are coated by the N-propenyl aniline monomer and can generate copolymerization, wherein the inorganic nano smoke suppressant powder is used as the center; finally, 260g of 1, 3-butadiene and 170g of styrene are sequentially added, 1.5g of BPDH is added when the temperature is raised to 75 ℃, the reaction is carried out for 5.0hr, then 30g of diethylhydroxylamine is added, and the ultra-dispersed polymer functionalized nano smoke suppressant is prepared by washing, drying and grinding.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, sequentially adding 2500g of pentane, 760g of diethyl allyl phosphate, 240g of N-propenyl aniline and 3g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 1.6g of BPDH when the temperature of the polymerization kettle reaches 60 ℃, reacting for 6.0hr, then adding 80g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 60min, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: firstly, introducing inert gas into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2600g of pentane, 1000g of macromolecular phosphorus-nitrogen flame retardant, 0.9g of THF and 7.0mmo1 of n-butyllithium into the reaction kettle, heating to 65 ℃, and reacting for 65min to form [ -BR-]nMacromolecular "phosphorus-nitrogen" flame retardants for homopolymers; then adding 260g of styrene and 1.2g of THF into a polymerization kettle in sequence, heating to 75 ℃, reacting for 80min, adding 30g of methanol, discharging, washing and drying to obtain the high-molecular phosphorus-nitrogen flame retardant.
(3) The preparation of the nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following steps: 2000g of HIPS (492J), 210g of high-molecular phosphorus-nitrogen flame retardant, 160g of ultra-dispersed high-molecular functional nano smoke suppressant, 8g of zinc stearate and 10105 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 8min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 5min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 4
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the same as in example 3.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 3.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 3.
(3) The preparation of the nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following steps: 2000g of HIPS (492J), 260g of high-molecular phosphorus-nitrogen flame retardant, 170g of ultra-dispersed high-molecular functional nano smoke suppressant, 9g of zinc stearate and 10106 g of antioxidant are put into a 10L high-speed mixer together to be mixed at high speed for 6min, finally, the mixed materials are added into a phi 34 double-screw extruder, and the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 5
(1) Ultra-dispersed polymer functionalized composite nano smoke suppressant: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of pentane and 50g of ethylenediamine into the polymerization kettle, adjusting the pH value of a system to be 9.0 by using sodium hydroxide, adding 1000g of nano white carbon black and 50g of KH-550 into the polymerization kettle when the temperature is raised to 60 ℃, stirring and mixing for 2.0 hours, then adding 100g of N-propenyl aniline, stirring and mixing for 3.0 hours to generate seeds which are coated by vinyl amide monomers and can generate copolymerization, wherein the inorganic nano smoke suppressant powder is used as the center; finally, 300g of 1, 3-butadiene and 200g of styrene are sequentially added, 2.6g of BPDH is added when the temperature is raised to 80 ℃, the reaction is carried out for 7.0hr, then 50g of diethylhydroxylamine is added, and the ultra-dispersed polymer functionalized composite nano smoke suppressant is prepared by washing, drying and grinding.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: firstly, introducing nitrogen into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of pentane, 800g of allyl diethyl phosphate, 200g of N-propenyl aniline and 5g of tert-dodecyl mercaptan into the polymerization kettle, stirring, mixing and heating, adding 2.0g of BPDH when the temperature of the polymerization kettle reaches 70 ℃, reacting for 7.0hr, then adding 100g of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 70min, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: firstly, introducing inert gas into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of pentane, 1000g of macromolecular phosphorus-nitrogen flame retardant, 1.2g of THF and 9.0mmo1 of n-butyllithium into the reaction kettle, heating to 70 ℃, and reacting for 70min to form [ -BR-]nMacromolecular "phosphorus-nitrogen" flame retardants for homopolymers; then adding 300g of styrene and 1.6g of THF into a polymerization kettle in sequence, heating to 80 ℃, reacting for 90min, adding 50g of methanol, finally discharging, washing and drying to obtain the high-molecular phosphorus-nitrogen flame retardant.
(3) The preparation of the nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following steps: 2000g of HIPS (492J), 280g of high molecular phosphorus-nitrogen flame retardant, 180g of ultra-dispersed high molecular functional nano smoke suppressant, 10g of zinc stearate and 10107 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 9min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 6min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Example 6
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the same as in example 5.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 5.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 5.
(3) The preparation of the nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following steps: 2000g of HIPS (492J), 300g of high molecular phosphorus-nitrogen flame retardant, 200g of ultra-dispersed high molecular functional nano smoke suppressant, 12g of zinc stearate and 10109 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 6min, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 1
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the other conditions are the same as the example 1, except that the preparation process of the ultra-dispersed polymer functionalized nano smoke suppressant does not add ethylenediamine, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 2 times, adding 2000g of pentane into the polymerization kettle, adjusting the pH value of the system to be 8.0 by using sodium hydroxide, adding 1000g of nano white carbon black and 10g of KH-550 when the temperature is raised to 50 ℃, stirring and mixing for 1.0hr, then adding 50g of N-propenyl aniline, stirring and mixing for 2.0hr to generate seeds which are coated by the N-propenyl aniline monomer and take copolymerization and take place and take inorganic nano smoke suppressant powder as the center; finally, 200g of 1, 3-butadiene and 100g of styrene are sequentially added, 0.5g of BPDH is added when the temperature is raised to 70 ℃, the reaction is carried out for 5.0hr, then 10g of diethylhydroxylamine is added, and the ultra-dispersed polymer functionalized nano smoke suppressant a is prepared by washing, drying and grinding. .
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 1.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 1.
(3) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: the difference lies in that in the preparation process of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin, the ultra-dispersed high-molecular functionalized nano smoke suppressant a is not added, and the addition amount is 100g, namely: 2000g of HIPS (492J), 100g of high-molecular phosphorus-nitrogen flame retardant, 100g of ultra-dispersed high-molecular functional nano smoke suppressant a, 6g of zinc stearate and 10104 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 5min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 2
(1) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 2.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 2.
(2) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: the difference lies in that the ultra-dispersed high molecular functional nano smoke suppressant is not added in the preparation process of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin, but the nano white carbon black is directly added, the addition amount is 130g, namely: 2000g of HIPS (492J), 150g of high-molecular phosphorus-nitrogen flame retardant, 130g of nano white carbon black, 8g of zinc stearate and 10105 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 6min at high speed, finally, the mixed materials are added into a phi 34 twin-screw extruder, and the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 3
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the other conditions are the same as example 3, except that the amount of N-propenyl aniline added in the preparation process of the ultra-dispersed polymer functionalized composite nano smoke suppressant is 20g, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 3 times, sequentially adding 2600g of pentane and 30g of ethylenediamine into the polymerization kettle, adjusting the pH value of a system to be 8.5 by using sodium hydroxide, adding 640g of aluminum hydroxide, 360g of aluminum hypophosphite and 20g of KH-560 when the temperature is raised to 55 ℃, stirring and mixing for 1.5 hours, then adding 20g of N-propenyl aniline, stirring and mixing for 2.6 hours to generate seeds which are coated by the N-propenyl aniline monomer and can generate copolymerization, wherein the inorganic nano smoke suppressant powder is used as the center; finally, 260g of 1, 3-butadiene and 170g of styrene are sequentially added, 1.5g of BPDH is added when the temperature is raised to 75 ℃, the reaction is carried out for 5.0hr, then 30g of diethylhydroxylamine is added, and the ultra-dispersed polymer functionalized nano smoke suppressant b is prepared by washing, drying and grinding.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 3.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 3.
(3) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: the difference lies in that in the preparation process of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin, the ultra-dispersed high-molecular functionalized nano smoke suppressant b is not added, and the addition amount is 160g, namely: 2000g of HIPS (492J), 210g of high-molecular phosphorus-nitrogen flame retardant, 160g of ultra-dispersed high-molecular functional nano smoke suppressant b, 8g of zinc stearate and 10105 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 8min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 5min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 4
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the same as in example 4.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 4.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 4.
(3) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: the difference lies in that the adding amount of the ultra-dispersed high molecular functional nano smoke suppressant is 60g in the preparation process of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin, namely: 2000g of HIPS (492J), 260g of high-molecular phosphorus-nitrogen flame retardant, 60g of ultra-dispersed high-molecular functional nano smoke suppressant, 9g of zinc stearate and 10106 g of antioxidant are put into a 10L high-speed mixer together to be mixed at high speed for 6min, finally, the mixed materials are added into a phi 34 double-screw extruder, and the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 5
(1) Ultra-dispersed polymer functionalized composite nano smoke suppressant: the other conditions are the same as the example 5, except that 1, 3-butadiene is not added in the preparation process of the ultra-dispersed polymer functionalized nano smoke suppressant, namely: firstly, introducing argon into a 15L stainless steel reaction kettle with a jacket for replacement for 4 times, sequentially adding 3000g of pentane and 50g of ethylenediamine into the polymerization kettle, adjusting the pH value of a system to be 9.0 by using sodium hydroxide, adding 600g of aluminum hydroxide, 400g of aluminum hypophosphite and 50g of KH-560 when the temperature is raised to 60 ℃, stirring and mixing for 2.0 hours, then adding 100g of N-propenyl aniline, stirring and mixing for 3.0 hours to generate seeds which are coated by the N-propenyl aniline monomer and can generate copolymerization, wherein the inorganic nano smoke suppressant powder is used as the center; finally, 200g of styrene is sequentially added, 2.6g of BPDH is added when the temperature is raised to 80 ℃, the reaction is carried out for 7.0h, 50g of diethylhydroxylamine is added, and the ultra-dispersed polymer functionalized nano smoke suppressant c is prepared by washing, drying and grinding.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 5.
b, preparation of a high molecular phosphorus-nitrogen flame retardant: the same as in example 5.
(3) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: the difference lies in that in the preparation process of the environment-friendly flame-retardant low-smoke high-impact polystyrene resin, the ultra-dispersed high-molecular functionalized nano smoke suppressant c is not added, and the addition amount is 180g, namely: 2000g of HIPS (492J), 280g of high molecular phosphorus-nitrogen flame retardant, 180g of ultra-dispersed high molecular functional nano smoke suppressant c, 10g of zinc stearate and 10107 g of antioxidant are put into a 10L high-speed mixer together to be mixed for 9min at high speed, and finally the mixed materials are added into a phi 34 double-screw extruder, wherein the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 6min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
Comparative example 6
(1) Ultra-dispersed polymer functionalized nano smoke suppressant: the same as in example 6.
(2) Preparation of high molecular phosphorus-nitrogen flame retardant:
a, preparing a macromolecular 'phosphorus-nitrogen' flame retardant: the same as in example 6.
(3) Preparation of environment-friendly flame-retardant low-smoke high-impact polystyrene resin: the difference lies in that in the preparation process of the environment-friendly flame-retardant, low-smoke and high-impact polystyrene resin, a macromolecular phosphorus-nitrogen flame retardant is not added, but only added, the addition amount of the macromolecular phosphorus-nitrogen flame retardant is 300g, namely: 2000g of HIPS (492J), 300g of macromolecular phosphorus-nitrogen flame retardant, 200g of ultra-dispersed macromolecular functionalized nano smoke suppressant, 12g of zinc stearate and 10109 g of antioxidant are put into a 10L high-speed mixer together for high-speed mixing for 6min, finally, the mixed materials are added into a phi 34 twin-screw extruder, and the reaction temperature (DEG C) of each section of the screw is as follows in sequence: 160, 170, 180, 185, 190, 200, 195, 185, 175; and performing extrusion reaction for 4min, and then performing extrusion, cooling and granulation to obtain the environment-friendly flame-retardant high impact polystyrene resin. Sampling and analyzing: standard test specimens were prepared and the test properties are shown in Table 1.
TABLE 1 Properties of environmentally friendly flame retardant, Low Smoke, high impact polystyrene resin
Reference sample*: polystyrene (492J) commercially available from Yanshan petrochemical company, China petrochemical.
Claims (31)
1. A nano-scale ultra-dispersed environment-friendly flame-retardant low-smoke high-impact polystyrene resin composition comprises the following components in parts by mass:
(1) 100 parts of high impact polystyrene resin; (2) 5-15 parts of a high-molecular phosphorus-nitrogen flame retardant; (3) 5-10 parts of a super-dispersed polymer functionalized nano smoke suppressant; (4) 0.2-0.6 part of a stabilizer; (5) 0.1-0.5 part of antioxidant, which is characterized in that:
the ultra-dispersed high-molecular functionalized nano smoke suppressant is a core-shell structure substance which takes the nano smoke suppressant as a core and takes a block copolymer of poly-conjugated diene and aryl ethylene as a shell;
the structural general formula of the macromolecular phosphorus-oxygen flame retardant is as follows:
in the formula: r is C1～C8PS is a homopolymer of styrene; BR is a homopolymer of 1, 3-butadiene, and m, n, h and L are the number of repeating units.
2. The nano-scale ultra-dispersed environment-friendly flame-retardant, low-smoke and high-impact polystyrene resin composition as claimed in claim 1, wherein the nano smoke suppressant 1 is one selected from carbon nanotubes, graphene oxide or nano white carbon black.
3. The nano-scale ultra-dispersed environment-friendly flame-retardant, low-smoke and high-impact polystyrene resin composition as claimed in claim 3, wherein said nano smoke suppressant 1 is nano white carbon black.
4. The nano-sized ultra-dispersed environment-friendly flame-retardant, low-smoke, high-impact polystyrene resin composition as claimed in claim 1, wherein said nano smoke suppressant 2 is an inorganic hypophosphite selected from one of zinc hypophosphite, aluminum hypophosphite, calcium hypophosphite, magnesium hypophosphite.
5. The nano-scale ultra-dispersed environment-friendly flame-retardant, low-smoke, high-impact polystyrene resin composition as claimed in claim 1, wherein said nano smoke suppressant 2 is aluminum hypophosphite.
6. The nano-scale ultra-dispersed environment-friendly flame-retardant, low-smoke and high-impact polystyrene resin composition as claimed in claim 1, wherein the high-impact polystyrene resin is a copolymer of styrene and polybutadiene rubber, and the melt flow rate is 0.5-20 g/10 min.
7. A process for preparing a polymeric phosphorus-nitrogen flame retardant as claimed in claim 1, which comprises the steps of:
(1) preparing a macromolecular phosphorus-nitrogen flame retardant: taking the total mass of allyl phosphate diester and vinyl amide as 100 parts, sequentially adding 200-300 parts of solvent, 70-80 parts of allyl phosphate diester, 20-30 parts of vinyl amide and 0.1-0.5 part of molecular weight regulator into a polymerization kettle which is subjected to inert gas replacement, stirring, mixing and heating, adding 0.05-0.5 part of initiator a when the temperature of the polymerization kettle reaches 60-70 ℃, reacting for 5.0-7.0 hr, adding 1.0-5.0 parts of 1, 3-butadiene into the polymerization kettle for end capping, reacting for 50-70 min until no free monomer exists, washing and drying to obtain the macromolecular phosphorus-nitrogen flame retardant with reaction activity;
(2) preparing a high-molecular phosphorus-nitrogen flame retardant: based on 100 parts of the total mass of the macromolecular phosphorus-nitrogen flame retardant, passing through inert gasSequentially adding 200-300 parts of solvent, 100 parts of macromolecular phosphorus-nitrogen fire retardant, 0.05-0.1 part of structure regulator and initiator b into the polymerization kettle after the body replacement, heating to 60-70 ℃, and reacting for 50-80 min to form [ -BR-]nMacromolecular phosphorus-nitrogen flame retardants of homopolymer chain segments; and then sequentially adding 20-30 parts of styrene and 0.05-0.2 part of structure regulator into the polymerization kettle, heating to 70-80 ℃, reacting for 70-90 min, adding 1.0-5.0 parts of terminator, finally discharging, washing and drying to obtain the high-molecular phosphorus-nitrogen flame retardant.
8. The method according to claim 7, wherein the allyl phosphate diester is one of dimethyl allyl phosphate, diethyl allyl phosphate, dipropyl allyl phosphate, dibutyl allyl phosphate, dipentyl allyl phosphate, dihexyl allyl phosphate, diheptyl allyl phosphate and dioctyl allyl phosphate.
9. The method for producing a polymeric phosphorus-nitrogen flame retardant according to claim 8, wherein the allyl phosphate diester is diethyl allyl phosphate.
10. The method according to claim 7, wherein the molecular weight modifier is selected from the group consisting of tert-dodecyl mercaptan, tert-tetradecyl mercaptan, and tert-hexadecyl mercaptan.
11. The method of claim 10, wherein the molecular weight regulator is t-dodecyl mercaptan.
12. The method according to claim 7, wherein the initiator a is an organic peroxide selected from the group consisting of di-t-butyl hydroperoxide, 2, 5-dimethyl-2, 5-di-t-butyl hexane peroxide, di-t-butyl peroxide and dicumyl peroxide.
13. The method for preparing a polymeric phosphorus-nitrogen flame retardant according to claim 12, wherein the initiator a is 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane.
14. The method according to claim 7, wherein the initiator b is selected from the group consisting of n-butyllithium, sec-butyllithium, methylbutyllithium, phenylbutyllithium, naphthyllithium, cyclohexyllithium, and dodecyllithium.
15. The method for producing a polymeric phosphorus-nitrogen flame retardant according to claim 14, wherein the initiator b is n-butyllithium.
16. The method according to claim 7, wherein the structure-controlling agent is one selected from the group consisting of diethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, ethyl methyl ether, anisole, diphenyl ether, ethylene glycol dimethyl ether, and triethylamine.
17. The method according to claim 16, wherein the structure-controlling agent is tetrahydrofuran.
18. The method of claim 7, wherein the vinyl amide is selected from the group consisting of acrylamide, methacrylamide, 1-butenamide, methacrylamide, 1-hexenamide, and propenyl-N-aniline.
19. The method of claim 18, wherein the vinyl amide is N-propenyl aniline.
20. A method for preparing the ultra-dispersed polymer functionalized nano smoke suppressant as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps: adding 300-400 parts of solvent and 1-5 parts of polyamine into a polymerization kettle which is subjected to inert gas replacement in sequence according to 100 parts of total mass of the nano smoke suppressant, adjusting the pH value of a system to be 8.0-9.0 by using a buffering agent, adding 60-70 parts of nano smoke suppressant 1, 30-40 parts of nano smoke suppressant 2 and 1.0-3.0 parts of silane coupling agent when the temperature is raised to 50-60 ℃, stirring and mixing for 1.0-2.0 hours, then adding 5-10 parts of vinyl amide, stirring and mixing for 2.0-3.0 hours to generate seeds which are coated by vinyl amide monomers and can be copolymerized by taking inorganic nano smoke suppressant powder as the center; finally, sequentially adding 20-30 parts of conjugated diene and 10-20 parts of aryl ethylene compound, heating to 70-80 ℃, adding 0.05-0.3 part of the initiator according to any one of claims 7 and 12-13, reacting for 5.0-7.0 hr, then adding 1-5 parts of terminator, washing, drying and grinding to obtain the ultra-dispersed high-molecular functionalized composite nano smoke suppressant.
21. The method of claim 20, wherein the polyamine is selected from the group consisting of ethylenediamine, triethylamine, diethylenetriamine, hexamethylenetetramine, and isophoronediamine.
22. The method of claim 21 wherein the polyamine is ethylenediamine.
23. The method of claim 20, wherein the silane coupling agent is selected from the group consisting of gamma-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, N-beta-aminoethyl-gamma-aminopropylmethyldimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltris (beta-methoxyethoxy) silane.
24. The method of claim 23, wherein the silane coupling agent is gamma-aminopropyltriethoxysilane.
25. The method of claim 20, wherein the conjugated diene is selected from the group consisting of 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2, 3-diethyl-1, 3-butadiene, 2-methyl-3-ethyl-1, 3-butadiene, 1, 3-pentadiene, 3-butyl-1, 3-octadiene; 1, 3-hexadiene.
26. The method of claim 25, wherein the conjugated diene is 1, 3-butadiene.
27. The method of claim 20, wherein the arylethenoid compound is one of styrene, alpha-methylstyrene, and 2-phenylpropylene.
28. The method of claim 27, wherein the aryl vinyl compound is styrene.
29. A method for preparing the nano-scale ultra-dispersed environment-friendly flame-retardant, low-smoke and high-impact polystyrene resin composition as claimed in claim 1, which is characterized in that the preparation process comprises the following steps: taking 100 parts of high impact polystyrene resin as a reference, uniformly mixing 100 parts of high impact polystyrene resin, 5-15 parts of high molecular phosphorus-nitrogen flame retardant, 5-10 parts of ultra-dispersed high molecular functional composite nano smoke suppressant, 0.2-0.6 part of stabilizer and 0.1-0.5 part of antioxidant, directly adding the mixture into a screw kneading machine, reacting at the temperature of 160-200 ℃, reacting, extruding, cooling and granulating to obtain the nanoscale ultra-dispersed environment-friendly flame-retardant low-smoke high impact polystyrene resin composition.
30. The method of preparing an environmentally friendly flame retardant, low smoke high impact polystyrene resin composition of claim 29, wherein said screw kneader is selected from the group consisting of a single screw extruder and a multi-screw extruder.
31. The method of preparing an environmentally friendly flame retardant, low smoke high impact polystyrene resin composition of claim 30, wherein said screw kneader is a twin screw extruder.
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